Synergistic antioxidant containing amino acids



Patented Aug. 8, 195 t v 7 2,518,233 A N SYNERGISTIC mroxmanr CONTAINING it "Amoacms Lloyd A. Hall, Chicago,lll., asslgnorto 1' 1 1 The Grimth Laboratories, Inc. 1,, g

No Drawing. Application September 11,1940, 1 Serial No. 696,338 p l This invention relates to an antioxidant and more particularly to an antioxidant composition with non-toxic properties containing amino acids and employed for preserving and stabilizing such food substances as lard, oleo oil, butter, peanut butter, mayonnaise, cheese spreads, vegetable oils, fish oils, hydrogenated fats, milk powders, egg powder, sausage, bacon, oil soluble vitamins, chocolate, cocoa, cocoa butter, coconut fats, essential oils, margarine, lanolin and other fatty food products or food products containing large amounts of fatty matter which are subject to rancidity development.

The invention is further characterized by the action of small amounts of two or more materials which, when used together, exert a synergistic antioxidant actioni. e., an anti-oxygenic eflect greater than the sum of the anti-oxygenic eflects, if any, of the individual materials when used separately.

Oils and fats often become rancid, which in the case of otherwise edible products, renders them unfit for human consumption. Some of the constituents of oils and fats are known to possess the tendency to absorb or react with oxygen. Thus, rancidity development results primarily from the products formed during oxidation. The dissolved or absorbed oxygen usually reacts first to form peroxides and the development of peroxides may be further accelerated by moisture, heat, light or catalyst. Aldehydes, ketones, and acids of lower molecular weight may be formed in the further decomposition and these materials also impart an undesirable odor or taste to the oil, fat or food product. The evaluation of rancidity is carried out by what is referred to as the Active Oxygen Method (AOM). It pertains to the amount of peroxides developed per kilogram of fat under standard conditions of acceleration. This test is also sometimes called the Swift Stability Test. Figures greater than those for the control indicate antioxidant value.

A great deal of work has been done on antioxidants for use in food products and particularly in animal fats' such as lard. Some of the suggested materials have been highly successful, but extremely expensive. Some of the most effective materials have had to be incorporated in a volatile solvent, the removal of which is expensive and cannot be accomplished at most small rendering plants. Some of the suggested products havebeen toxic and unfit for use in food. The use of vegetable oils in antioxidant preparations has been suggested, but it has been necessary to use these oils in such quantity as 6 Claims. (01. 260-3985) to seriously lower the melting point of the lard mixtures. I have found that some amino acids 7 can be used in synergistic mixtures to extend the keeping time and preservation of fats and oils and other food materials and thus are unusually effective antioxidants.

The following, table, shows the AOM value of prime steam lard and kettle rendered lard when antioxidant amino acids are used in a ratio of Table I AOM at 208 F.

Prime Kettle Steam Rendered 14rd Lard A nninv It will be noted that the amino acid'in Table I give antioxidant-efiects when used separately. Other amino acids, such as cystine, valine, serine, aspartic acid, glutamic acid, and prollne do not appear to have antioxidant properties either where used separately or in synergistic mixtures. Several of the amino acids have fairly high antioxidant values, namely, methionine, tryptophane, glycine, arginine, phenylalanine, and threonlne.

The following table gives data on synergistic mixtures of several of the amino acids with lecithin in lard:

Table II AOM hours at 208 F. Control lard f 4 0.10% lecithin 7 0.25% tryptophane+0.10% lecithin 25 0.25% methionine+0.l0% lecithin 29 other ester of a higher fatty acid. Lecithin. preferably in the crude form is employed in an amount from about five per cent to 30 per cent of the antioxidant mixture. 1 have now discovered that amino acids enhance the emciency of these synergistic antioxidant mixtures. In the following table I give the composition and formulae of several examples and antioxidant data:

Table III $1 Antioxidant and Composition 2E 2"; flat? ControlLar 2 4 B 1 i .337 0.0033 1 r g i 311111131: 50.01% 0. 0001 2---. Butyl e----.. 1.00% 0.00125 10 Pro 1 to 2.007 0.00250 recfiinmhnuunnnn 17.00% 0.02125 Gem Oil 80.00% 0.01000 3 4.--... Butyl Tyroeine.--- l.

Pro 1 Gallete 2. 0. 13 Leci 10. 5 0.02000 Corn 0il. 80 60% 0.10003 In examples 1 and 6, the synergistic antioxidant is a crystalline powder, which is simply dissolved in the product to be stabilized, for instance lard, by agitation and heating at about 210 to 220 F. In the other examples, the various ingredients are solubilized in corn or other suitable vegetable oil with the aid of heat to 220 F. and agitation. Corn, peanut, and other vegetable oils contain small. amounts of tocopherols which give some synergistic antioxidant properties in my above formulae. Thus, all my synergistic antioxidant compositions in Table III are liquids except 1 and 6. They are added to the material to be stabilized at any desirable point at temperatures not exceeding 240 F. by agitation. In the case of addition to lard, my liquid synergistic antioxidants are preferably mixed into the refined lard at 140 to 150 F. before it goes to the lard roll or votator. There is no separation of the antioxidant when the lard is cooled, no taste or odor imparted and no efi'ect on melting point when my synergistic antioxidants are used in the amount of 0.125% to 0.500%. Neither is there substantial decomposition of the antioxidant in fats, such as lard, at baking or cooking temperatures to 375 F. v

In certain instances a vegetable 011 should not be included in a synergistic antioxidant mixture for the reason that it may lower the melting point of the fat in which this type 01 filltiolsiqant is used. For this reason, I have made synergistic antioxidant mixtures using lard and a hydrogenated cotton seed oil as a part of the i'ormula for my new synergistic antioxidant. Data is given or these compositions in the following examples:

Table IV Per Cent AOM Hours ample Antioxidant and Composition m m at I- 2..... Glycine 0.025% 0.00313 24 Pro yI Gallate---- 0. 62%; 0. 00313 Hy enated Fet..--. 98. 75 o 0. 40374 8...... Pro i Gallate.- 0. 6257 0.00313 28 LecRKin..-- 4.0009 0.02000 H Lard 05.33% 0. 47087 33 Prop 1 Gallate--- Lecit ln..-.-----....---- 8. 0 0.04000 Hydrogenated Fat..-..- 00.75 a 0. 45375 0.00313 34% 0.00313 0 t 4. 0 0.02000 Hydrogenated Fat.. 94.75% 0. 47375 The products in the synergistic mixtures in Table IV were made by weighing out the required amount of materials, then adding the melted lard or hydrogenated fat at about F.. stirring rapidly at first to get a uniform mixture and then stirring very slightly until the lard or hydrogenated fat congealed. The synergistic mixtures made with lard or hydrogenated rat were used as antioxidants on the basis of 0.50% but the respective amounts of glycine and propyl gallate are the same in each example formula. Lecithin.

citric acids produce the synergistic eflects inv combination with the antioxidants herein disclosed, as well as with other substances as to which reterence is made to my accompanying application, Serial No. 696,339. filed September 11, 1946, now Patent No. 2,511,802.

The following table illustrates examples of the use 0! such acids.

Table V E 5 Antioxidant and Composition g f {3%5? Control Lar 00000 15% 00000 0. 0010 4-.-.- Glycine 05.007 0.0000 10% Propyl Gallate 65. 0 0.0065

Benmic Acid 0. 0100 Bu 11 e... 03. 007 0.0033 20 Pro g i 5m 0a007 0.0005 Fumaric Acid. 2.00% 0.0002

0. Pro 100mm 2. 757 0.0043 22% Leciil m 0.00344 Refined Corn 011--..--" 70. 50% 0. 09913 Glycine 0.0500

s-- Propyl Gal1ate. 0. 0100 25 9.- Pro lGallate 0. 0100 20 Ben zgic Acid 0. 0100 10..., Glycine 0.0000 20 Propyl (1011000.--- 00.00 0 0.0060 Benzoic Acid. 10007, 0.0010

11.-.. Glycine 30.00% 0.0080 26% Pr lGallate .007 0.0000 Acid. 10. 007; 0. 0010 12-.-. Pro 10011000 2. 757 0. 00343 21 Lecithimnnnnnnun 20. 707:, 05044 Refined Corn 0il.- 70. 50% 0. 00913 Glycine 0.0100

15.... G1 cine 35.007 0.0005 07 Prgpyl Gallate 05.007: 0.0005

Citric Acid 0. 0100 16-... Pro 1 Gallate .0100 48% magnum"------------ 0. 0100 The examples in Table V are crystalline powin which a tocopherol containing vegetable oil, such as corn oil, is employed as a solubilizing agent or carrier. In these cases the ingredients may be mixed together and heated at 150 F.,

with agitation until dissolved.

It is apparent from the foregoing that various synergistic compositions comprising amino acids can be used to advantage as antioxidants. While a number of amino acids can be used in such synergistic antioxidants, I prefer to use glycine, in combination with propyl gallate, lecithin and tocopherols. I have chosen glycine as my preferred amino acid because of cost, availability and its excellent stabilizing and preservative qualities. I have also used as one of my synergists, the esters 01' some of the amino acids, such as butyl tyrosine. The synergistic action of amino acid esters have thus been proven valuable as antioxidant materials. The synergistic antioxidants of the present invention not only are relatively inexpensive, but they can be used easily by simply distributing them through the product to be stabilized without the necessity of a special solvent or expensive process or equipment.

The foregoing detailed description is given for clearness of understanding only, and no unnecessary limitations should be understood therefrom, for some modifications will be obvious to those skilled in the art.

I claim:

1. A fatty composition consisting predominantly of glycerides of fatty acid and containing not substantially more than 0.25% of an antioxidant composition comprising a synergistic mixture of an amino acid compound of the class consisting of glycine, threonine, phenylalanine, arginine, methionine, tryptophane, tyrosine, butyl tyrosine, and alanine; a gallic acid ester and an organic acid of the class consisting of benzoic, fumaric, tartaric and citric.

2. A composition as set forth in claim 1 in which the gallic acid ester is propyl gallate.

3. A composition as set forth in claim 1 in which the organic acid is citric acid.

4. A composition comprising approximately 35 parts of glycine, 65 parts of propyl gallate and parts of citric acid.

5. An antioxidant composition comprising an amino acid compound of the class consisting of glycine, threonine; phenylalanine, arginine, methionine, tryptophane, tyrosine, butyl tyrosine and alanine; an organic acid of the class consisting of benzoic, fumaric, tartaric and citric: an ester of the class consisting of gallic acid esters and ascorbyl esters; and lecithin, said amino acid, organic acid, ester and lecithin being present in such proportions as to give a synergistic effect in said antioxidant composition.

6. An antioxidant composition comprising an amino acid compound of the class consisting of glycine, threonine, phenylalanine, arginine, methionine, tryptophane, tyrosine, butyl tyrosine and alanine; an organic acid of the class consisting of benzoic, fumaric, tartaric and citric; an ester of the class consisting of gallic acid esters and ascorbyl esters; said amino acid, organic acid and ester being present in such proportions as to give a synergistic efl'ect in said antioxidant composition.

LLOYD A. HALL.

(References on following page) 7 REFERENCES crrEn Number The following references are of record in the file of patent: UNITED STATES PATENTS I 2,383,815

Number Name Date 1,869,469 Divine Aug. 1932 2397320 2,047,642 Marvel July 4, 1938 Name Date Bohm et a1 Nov. 26, 1940 Musher July 14, 1942 Norris May 29, 1945 Riemenschneider et a1. Aug. 28, 1945 One et a1. Apr. 9, 1946 

1. A FATTY COMPOSITION CONSISTING PREDOMINANTLY OF GLYCERIDES OF FATTY ACID AND CONTAINING NOT SUBSTANTIALLY MORE THAN 0.25% OF AN ANTIOXIDANT COMPOSITION COMPRISING A SYNERGISTIC MIXTURE OF AN AMINO ACID COMPOUND OF THE CLASS CONSISTING OF GLYCINE, THREONINE, PHENYLALANINE, ARGININE, METHIONINE, TRYPTOPHANE, TYROSINE, BUTYL TYROSINE, AND ALANINE; A GALLIC ACID ESTER AND AN ORGANIC ACID OF THE CLASS CONSISTING OF BENZONIC, FUMARIC, TATARIC AND CRITIC. 